CN105190836A - Copper-indium-gallium-chalcogenide nanoparticle precursors for thin-film solar cells - Google Patents

Copper-indium-gallium-chalcogenide nanoparticle precursors for thin-film solar cells Download PDF

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CN105190836A
CN105190836A CN201480025307.5A CN201480025307A CN105190836A CN 105190836 A CN105190836 A CN 105190836A CN 201480025307 A CN201480025307 A CN 201480025307A CN 105190836 A CN105190836 A CN 105190836A
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nano particle
mercaptan
temperature
cuins
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詹姆斯·哈里斯
克里斯托弗·纽曼
翁布雷塔·马萨拉
劳拉·怀尔德
奈杰尔·皮克特
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Nanoco Technologies Ltd
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Abstract

Nanoparticles containing lUPAC group 11 ions, group 13 ions and sulfur ions are synthesized by adding metal salts and an alkanethiol in an organic solvent and promoting the reaction by applying heat. Nanoparticles are formed at temperatures as low as 200 DEG C. The nanoparticles may be thermally annealed for a certain amount of time at a temperature lower than the reaction temperature (usually about 40 DEG C lower) to improve the topology and narrow the size distribution. After the reaction is complete, the nanoparticles may be isolated by the addition of a non-solvent and re-dispersed in organic solvents including toluene, chloroform and hexane to form a nanoparticle ink. Additives may be incorporated in the reaction solution to tailor the final ink viscosity.

Description

For the copper-indium-gallium-chalcogenide nanoparticle precursor of thin-film solar cells
The cross reference of related application: the application is the non-provisional application of the U.S. Provisional Patent Application 61/772,372 that on March 4th, 2013 submits to, and its full content is combined in herein by reference.
Background
1. invention field
The present invention relates to photovoltaic material.More specifically, it relates to CuIn xga 1-xs 2the manufacture of (0≤x≤1) nano particle.
2. comprise the explanation of the correlation technique of information disclosed in 37CFR1.97 and 1.98
In order to viable commercial, photovoltaic cell must generate electricity with the cost of energy and fossil fuel competition.Lower cost materials must be used and manufacture photovoltaic cell by cheap apparatus manufacturing process.Photovoltaic cell must can have the conversion efficiency of moderate paramount sunlight to electricity.And materials synthesis and device fabrication must be all commercial-scale.
Photovoltaic market accounts for leading by silicon wafer system solar cell (being also called first generation solar cell) at present.Active layer in these solar cells is make from the silicon single crystal wafer of the thickness of several microns to hundreds of microns by having typical range, and this thickness is relatively large.Because silicon is relatively weak in absorption light, so need thick active layer.The manufacture of these single-crystal wafers is relatively costly, manufactures because its process comprises and cuts highly purified monocrystalline silicon cast ingot.The output of this process is normally low.
The high cost of crystal silicon wafer has impelled industrial quarters to find the more cheap material for solar cell.Semi-conducting material is curing/copper indium diselenide/gallium CuIn such as xga 1-xs 2(0≤x≤1) (being commonly referred to CIGS in this article) is strong light absorber and has the band gap with the optimal spectrum scope matched well of photovoltaic application.In addition, because these materials have strong absorptivity, the active layer in the solar cell using these materials only needs several micron thickness.
Two copper indium diselenide (CuInSe 2) be one of the most promising material standed for for film photovoltaic application.But, by by CuInS 2film selenizing can manufacture based on CuInSe 2solar cell.During selenizing, by CuInS 2film heats in rich selenium atmosphere, makes seleno to replace in film sulphur in some or all position, creates volumetric expansion because replace when Se replaces S, which reduces the void space in film and repeatedly can form the CuInSe of high-quality, densification 2absorber layer.Suppose to replace S with Se completely, it is about 14.6% (based on chalcopyrite (four directions) CuInS that gained cell volume expands 2lattice parameter and CuInSe 2lattice parameter calculate).Can by under rich selenium atmosphere by film annealing with by CuInS 2film of nanoparticles is converted into main selenide material.CuInS 2nano particle is hopeful as the manufacture of CuInSe 2the precursor of active layer.Use CuInS 2nano particle replaces only using CuInSe 2the advantage of nano particle is, sulphur precursor is usually more cheap than their selenium homologue and easilier obtain.
The optimum band gap of theory for absorber material is about 1.3-1.4eV.By gallium is attached to CuInS 2in nano particle, CuIn after band gap makes selenizing can be controlled xga 1-xse 2absorber layer has the optimum band gap for solar absorption.
Usually, by the gas phase of costliness or evaporation technique (such as Metalorganic chemical vapor deposition, RF sputtering, flash distillation etc.) for curing copper indium (gallium) film is deposited to substrate.Although those technology can manufacture high-quality film, for the processing output of scale to extensive deposition and Geng Gao, they are difficulty and costliness.
Use copper indium chalcogenide and/or copper indium gallium sulphur to belong to one of major advantage of the nano particle of compound to be, by nanoparticle dispersion in media as well, thus ink that is similar to the ink in newspaper type technique, that can print on substrate can be formed.The such as spin coating of low cost printing technology, slot coated or scraper for coating can be used nanoparticle inks or stick with paste deposition.Printable solar cell can replace that manufacture the standard of solar cell, conventional vacuum-deposited method, because typography, particularly when at roller-when carrying out in-roller process framework, much bigger output can be made to become possibility.
Utilized comprise hot injection method, the various synthetic methods of solvent heat technology and suitable precursor thermal decomposition have prepared ternary CuInS 2the nano particle of system.Colloidal nanoparticles synthesis uses high temperature (higher than 250 DEG C) to form little (<20nm), the nano particle of organic substance end-blocking usually.Like this, colloidal nanoparticles demonstrates the fusing point lower than block materials.Such nano particle has narrow fusion temperature scope usually, because nano particle is highly monodispersed (namely the diameter of nano particle is in narrow size distribution).Rare about CuInGaS 2and CuGaS 2the open source literature of the synthesis of nano particle, because most of open source literature pays close attention to ternary compound CuInS 2.
U.S. Patent application US2011/0039104A1 (' 104 application) from Bayer describes, for colloid synthesis CuInS 2the method of nano particle: use the reaction temperature between 240-270 DEG C with mantoquita, indium salt and alkanethiol in non-polar organic solvent.The method described in ' 104 applications does not prove to synthesize CuIn xga 1-xs 2the controllability of nano particle and can not prove that the selection adjusting original metal ratio and reagent can in order to obtain the stoichiometry expected.In addition, need higher boiling point mercaptan to use the reaction temperature described in ' 104 applications.
In another example, Kino etc. report by by Cu (OAc) 2with n (OAc) 3mix at 230 DEG C with 1-dodecyl mercaptans and tri-n-octyl amine and synthesize CuInS 2the method [T.Kino etc., Mater.Trans., 2008,49,435] of nano particle.Tri-n-octyl amine is height ligand solvent (having the boiling point of 365-367 DEG C), and the nano particle therefore likely using the method synthesis of Kito etc. is at least part of amine end-blocking.If described particle is used for photovoltaic device, this is disadvantageous, because need high processing temperature to remove amine from the film manufactured by nano particle.
Hot injection approach is usually by high temperature being formed by the solution that sulphur is injected into copper and indium salt at the solution of suitable solvent such as tri octyl phosphine (TOP) or oleyl amine (OLA).The CuInS of Zn doping has been manufactured at temperature by this method between 160-280 DEG C 2nano particle [H.Nakamura etc., Chem.Mater., 2006,18,3330].The shortcoming of hot injection technique is difficult to control reaction temperature on a large scale, so reaction is usually limited in milligram level and usually needs large reaction volume.
Single derived precursor (SSP) method for nano particle synthesis uses containing all single compounds of constitution element that will be added in nano particle.Under pyrolysis, SSP decomposes the formation causing nano particle.There is a large amount of list of references to describe and synthesize CuInS by SSP 2nano particle.By using (PR 3) 2cu (SR) 2in (SR) 2type precursor manufactures CuInS 2nano particle, wherein R is alkyl.Castro etc. are by the Liquid precursor (PPh in dioctyl phthalate 3) 2cuIn (SEt) 4decompose between 200-300 DEG C with the chalcopyrite CuInS of production size between 3-30nm 2nano particle [S.L.Castro etc., Chem.Mater., 2003,15,3142].Although their size is little, nano particle is insoluble in organic solvent because it forms the trend of large 500nm aggregation.
Dutta and Sharma makes the sulfonate precursor I n (S in spent glycol 2cOEt) 3with Cu (S 2cOEt) the cubic CuInS of the aggregation once in a while of average-size 3-4nm is obtained at 196 DEG C 2[D.P.Dutta and G.Sharma, Mater.Lett., 2006,60,2395].Because employ non-cooperation solvent, the CuInS manufactured by these SSP 2nano particle shows the dissolubility of non-constant and forms the tendency of micron order aggregation.SSP method is more complicated than additive method, because they need the step of extra synthesis precursor.
Additive method comprises makes slaine and sulphur source react.Choi etc. decompose copper by the dodecyl mercaptans be used at the temperature between 230-250 DEG C in OLA and indium metal oleate complex prepares Cu-In-S nano particle [S-H.Choi etc., J.Am.Chem.Soc., 2006,128,2520].In this process, synthesize before reacting with alkanethiol, be separated and purified metal oleate.Particle is sizable, and by change reaction time and temperature, shape of particle is adjusted to rubber fruit shape, doleiform and worm shape rod, length is between 50-100nm.But XRD analysis display nano particle is by the Cu of six harrisite structures 2the In of S and tetragonal 2s 3mixture composition instead of CuInS 2.Reaction in the toluene that Carmalt etc. are refluxed by metal chloride and vulcanized sodium at 110 DEG C manufactures micron-sized CuInS 2particle, but this material has very limited solubility [C.J.Carmalt etc., J.Mater.Chem., 1998,8,2209].
Using Study of way that solvent-thermal method synthesizes as nano particle.But domain size distribution is usually comparatively large and due to the formation nano particle normally indissoluble of aggregation.By mixed C uSO under the existence of TGA in autoclave 4, InCl 3micron order CuInS is prepared with thioacetamide 2particle [X.Guo etc., J.Am.Chem.Soc., 2006,128,7222].Lu etc. react to prepare cubic CuInS by making CuCl and metal In and sulphur powder in autoclave in a series of solvents comprising toluene, benzene and water at 200 DEG C 2nano particle [Q.Lu etc., Inorg.Chem., 2000,39,1606].Particle has the size between 5-15nm, but forms large aggregation and be insoluble.Toluene, benzene and water are used as reaction medium.TEM image demonstrates the control of the difference to domain size distribution, and domain size distribution changes according to reaction medium.In addition, Hu etc. report and use CuCl, GaCl 3with the CuGaS of thiocarbamide 2the solvent-thermal process [J.Q.Hu etc., SolidStateCommun., 2002,121,493] of nano particle.
Zhong etc. report CuGaS 2the synthesis [J.Zhong etc., Appl.Surf.Sci., 2011,257,10188] that the biomolecule of nano particle is auxiliary.By CuCl 2.2H 2o, GaCl 3with Cys (C 6h 12n 2o 4s 2) be dissolved in ethylenediamine and water, then at room temperature stir 20 minutes.In 10 hours, solution is heated to 200 DEG C in autoclave.Tem analysis shows the large nano particle of the average diameter with 600nm.
Although provide the synthetic method of level Four and more senior nano particle to there is sizable interest to exploitation, in prior art, only there is a few CuInS 2and/or CuGaS 2synthesis methods for nanoparticles is proved to be and is suitable for being provided in the CuIn across 0≤x≤1 scope xga 1-xs nano particle.Wang etc. describe the buergerite CuIn in scope 0≤x≤1 xga 1-xs 2colloid synthesis [Y-H.A.Wang etc., J.Am.Chem.Soc., 2011,133,11072] of nano particle.At room temperature by Cu (acac) 2, In (acac) 3, Ga (acac) 3stir in OLA with trioctyl phosphine oxide (TOPO) and use purging with nitrogen gas 30 minutes.Solution is heated to 150 DEG C, then 1-dodecyl mercaptans (DDT) and uncle-DDT is injected in solution fast, then it was heated to 280-290 DEG C in 30 minutes, then keep 30 minutes.Then hexane and ethanol is used to pass through centrifugation solution cool to room temperature.By replacing OLA with 1-vaccenic acid (ODE), nanoparticle morphology can be become tadpole shape from bullet shaped.Also the change of form can be observed when changing In:Ga ratio.Author claims that buergerite provides the stoichiometric flexibility controlling material mutually.
Although the method for the general introduction such as Wang may be used for synthesizing the CuIn across whole 0≤x≤1 scope xga 1-xs 2nano particle, but the following higher boiling point part end-blocking of nano particle: OLA (348-350 DEG C), TOPO (201-202 DEG C under 2mmHg, it is equivalent to 397-399 DEG C under atmospheric pressure), 1-DDT (266-283 DEG C) and/or uncle-DDT (227-248 DEG C).Thus need high-temperature service manufacturing technology to be removed by part from gained film.In addition, use the method for Wang etc., obtain CuInS 2rare buergerite phase.By contrast, current solar cell uses chalcopyrite as absorbent.
Chang etc. describe the Pyatyi Cu (In in the scope of 0≤x, y≤1 xga 1-x) (S yse 1-y) 2the synthesis of nano particle, it enables band gap adjust to 2.40eV [S-H.Chang etc., EnergyEnviron.Sci., 2011,4,4929] from 0.98.In typical reaction, by CuCl, InCl 3and/or GaCl 3, Se and/or S and OLA mixing, then use Ar purge 1 hour under 130 DEG C of vigorous stirring.Solution is heated to 265 DEG C then keep 90 minutes, will cancellation be reacted subsequently in cold bath.By with hexane/ethanol centrifugation product.For x, y ~ 0.5, average grain diameter is 16 ± 0.5nm, has irregular a little little form.Guo etc. report similar reaction.As x=1, synthesis has the colloid CuIn of the average grain diameter of 15nm xga 1-xs 2nano particle [Q.Guo etc., NanoLett., 2009,9,3060].In typical synthesis, by CuCl, InCl 3and/or GaCl 3to be dissolved in OLA and under Ar gas at 130 DEG C purge 30 minutes.Solution is heated to 225 DEG C, subsequently 1MS/OLA solution is injected fast.To react and keep 30 minutes at 225 DEG C, and then cool and pass through centrifugation by toluene/ethanol.Gained nano particle has low-down content of organics (<10%), makes them be insoluble to the organic and solvent of polarity and is difficult to as can printing ink processing.
By containing In and containing the combination of SSP of Ga for the synthesis of Cu (In, Ga) S 2nano particle.Sun etc. use two kinds of single source precursor (Ph of different proportion 3p) 2cu (μ-SEt) 2in (SEt) 2(Ph 3p) 2cu (μ-SEt) 2ga (SEt) 2mixture synthesis across the CuIn of 0≤x≤1 scope xga 1-xs 2nano particle [C.Sun etc., Chem.Mater., 2010,22,2699].In typical synthesis, by (Ph 3p) 2cu (μ-SEt) 2in (SEt) 2(Ph 3p) 2cu (μ-SEt) 2ga (SEt) 2be dissolved under the existence of 1,2-dithioglycol in benzyl acetate, then in microwave, 160 DEG C of irradiations are less than 1 hour.Microwave irradiation is used to provide the reaction temperature homogeneity higher than traditional thermal decomposition.The scope of diameter of nano particles is 2.7-3.3nm, and it increases with In content and increases, and band gap can be adjusted to 2.3eV (during x=0) from 1.59eV (during x=1).Increasing reaction temperature according to the show makes particle diameter increase and band gap is reduced.Although the SSP method that Sun etc. describe allows the ratio of adjustment In and Ga, Cu is determined by the stoichiometry of single source precursor with the ratio of (In+Ga) and can not be changed.
U.S. Patent number 7,892,519 describe for the manufacture of Cu (In, the Ga) S with mercaptides part end-blocking 2the SSP method of nano particle.But open text only illustrates synthesis CuInS 2method.
Liang etc. describe the CuIn be made up of the nanometer sheet that 15nm is thick 0.5ga 0.5s 2the solvent-thermal process [X.Liang etc., J.Alloys & Compounds, 2011,509,6200] of 1-2 μm of flower.In typical reaction, by CuCl 2.2H 2o, GaCl 3, InCl 3be dissolved in DMF by being stirred in 10 minutes with Cys.Solution is heated 10 hours at 220 DEG C in autoclave, then cool to room temperature.With deionized water by solids of sedimentation, then dry under vacuo.
Synthetic method described in the prior manufactures to have usually assembles tendency and the large nano particle be insoluble in most of solvent.This is important problem, because expect to manufacture little and solvable nano particle, it can be further processed with formulate ink, thus is such as printed by the conventional and technology of low cost or sprayed to manufacture inoranic membrane.Capping ligand such as hydrocarbon can be connected to contribute to processability with the surface of nano particle.But building-up process described above is at high temperature carried out, the selectional restriction of capping ligand is those parts with relative high evaporation/decomposition temperature by this.Because be difficult to remove part during film sintering, the existence of this type of low volatility capping ligand makes the use of the nano particle for the preparation of photovoltaic film complicated.The existence of the part be removed in film causes carbon back impurity, the performance of its negative effect film.
Since it is known method can not manufacture little and have low melting point, narrow size distribution nano particle and introduce and can give the volatility part of dissolubility and processability, these methods are not be very suitable for manufacturing the nano particle meeting conventional low cost film printing technology.In addition, verified seldom have method successfully can synthesize CuIn across whole 0≤x≤1 scope xga 1-xs 2nano particle.Object of the present disclosure addresses these problems.
General introduction
Method of the present invention produces the little CuInS with narrow size distribution 2and CuIn xga 1-xs 2nano particle (have diameter be low to moderate about 2.5nm and usually at about 2.5nm to the size within the scope of about 10nm).Can with volatility alkanethiol end-blocking nano particle and nano particle is solvable in a series of solvent.Can by nanoparticle dispersion in solvent such as toluene with formulate ink, can use that conventional low cost printing technology is such as sprayed, scraper for coating, rod painting, ink jet printing etc. by described deposit of ink to form CuInS 2or CuIn xga 1-xs 2film.
Use the nano particle of disclosed method manufacture usually to have lower fusing point compared with block materials and packaging is tightr, this contribute to melting during coalescent (coalescence) of particle, the film quality be improved.This allows lower processing temperature, makes to use flexible base, board (such as paper and plastics) to become possibility as the parts in PV battery.Because fusing point can along with change of size, the nano particle with narrow distribution of sizes will be similar to melting at that same temperature, manufacture high-quality film.
That it can by mild heat easily and remove from nano particle at an easy rate by the obvious advantage using low boiling alkanethiol to provide.This is important because from after the process of curing in film the carbon impurity of remaining part residue may cause the deterioration of solar cell properties.Another advantage is the effect that alkanethiol plays sulphur source and ligand thereof, this simplify synthesis.
Accompanying drawing is sketched
Fig. 1 shows the CuInS prepared by disclosed method 2the absorption spectrum of nano particle.
Fig. 2 shows the X-ray diffractogram of the nano particle prepared according to disclosed method.
Fig. 3 shows the CuInS prepared according to disclosed method 2the spectrum of nano particle.
Fig. 4 is the CuInS prepared according to disclosed method 2the transmission electron micrograph of nano particle.
Fig. 5 shows the CuInS prepared according to disclosed method 2the thermogravimetric analysis (TGA) of nano particle.
Fig. 6 shows the absorption spectrum of the nano particle prepared according to disclosed method.
Fig. 7 is the transmission electron micrograph of the nano particle prepared according to disclosed method.
Fig. 8 is the transmission electron micrograph of the nano particle prepared according to disclosed method.
Fig. 9 is the transmission electron micrograph of the nano particle prepared according to disclosed method.
Figure 10 is the CuInS prepared according to the embodiment of disclosed method 2the TGA of nano particle.
Figure 11 is the CuInS prepared according to the embodiment of disclosed method 2the absorption spectrum of nano particle and photoluminescence spectra.
Figure 12 is Cu (In, the Ga) S prepared according to the embodiment of disclosed method 2the TGA of nano particle.
Figure 13 is Cu (In, the Ga) S prepared according to the embodiment of disclosed method 2the absorption spectrum of nano particle and photoluminescence spectra.
Describe in detail
Disclosed in be method for the manufacture of the nano particle comprising the 11st race's ion [Cu, Ag or Au] and the 13rd race's ion [B, Al, Ga, In or Tl] and S ion.Preferred embodiment manufacture has formula CuIn xga 1-xs 2nano particle, wherein 0≤x≤1.As used in this article, formula CuInS 2refer to the material comprising Cu, In and S.Be understood that described formula must not represent that the ratio of Cu:In:S is strict 1:1:2.Equally, formula Cu (In, Ga) S 2refer to the material comprising Cu, In, Ga and S, but and the ratio of non-required Cu:In:Ga:S is strict 1:1:1:2.Term " CIGS " is in this article for limiting any material containing Cu and S and/or In and/or Ga.
Can be low to moderate at the temperature of less than 200 DEG C by the 11st race and the 13rd race's ion source and alkanethiol being reacted in organic solvent and pass through to apply heat to promote reaction and formed as nano particle disclosed in this article.11st race and the 13rd race's ion source normally slaine, the acetate of such as required metal ion or halogen.Can represent mercaptan compound with formula R-SH, wherein R replaces or unsubstituted organic group (namely one or more hydrogen atom be combined with carbon atom can be replaced by non-hydrogen atom).Organic group can be saturated or unsaturated.Organic group is preferably straight chain, side chain or cyclic organic group, and it can be carboxyl or heterocyclic radical.
Organic group is preferably alkyl, thiazolinyl, alkynyl and/or aryl.Organic group can be alkyl, the alkenyl or alkynyl of containing 2 to 20 carbon atoms, more preferably 4 to 14 carbon atoms and most preferably less than 10 carbon atoms.
Mercaptan plays two kinds of effects in synthesis.The first, they are sulphur sources of nano particle.The second, mercaptan plays surface conjunction part.Mercaptan is attached to the surface of nano particle, forms the ligand layer on surface.Ligand layer is almost special to be formed by mercaptan.In other words, a certain amount of solvent molecule can adhere to ligand layer or insert described layer, but most of ligand layer can be formed by mercaptan part.It is also to be understood that term " layer " non-required ligand layer are complete individual layers or are limited to an individual layer.Compared to independent individual layer, more or less thiol molecule may reside in nanoparticle surface.
It should be understood that disclosed method is that disclosed method operates at lower temperatures at present relative to the advantage of the method described in above background parts at present.Usually, the S source used in the synthesis of CIGS needs to be greater than the temperature of 200 DEG C to react.But disclosed method allows more lower boiling alkanethiol to be used as end-capping reagent between synthesis phase.
The use of low boiling mercaptan part is favourable, because it promotes that part removes from film at relatively low temperature.Low temperature removes and makes Cryo Equipment be processed into possibility.According to some embodiments, when nano particle is heated to more than 350 DEG C, from the mercaptan of nanoparticle surface ejection surface conjunction.As used in this article " ejection " can mercaptan decomposition be meant, evaporation or remove from nanoparticle surface.According to other embodiments, when nano particle is heated to more than 300 DEG C, more than 250 DEG C or more than 200 DEG C time, remove mercaptan.
According to different embodiments, alkanethiol can containing the carbon of less than ten, the carbon of the carbon of less than eight or less than six.Specially suitable alkanethiol is normal octane mercaptan, and it has the boiling point of about 200 DEG C.Alternatively, branched alkane mercaptan can be used, such as tertiary mercaptan.According to an embodiment, side chain mercaptan is used as sulphur source and short chain low boiling straight chain mercaptan is used as capping ligand.Tertiary mercaptan such as tertiary nonane mercaptan decomposes being equal to than its straight chain at the much lower temperature of mercaptan.Tertiary nonane mercaptan decomposes at ~ 100 DEG C.Thus, can synthesize at lower temperatures with the CIGS of tertiary mercaptan manufacture, allow to use short chain, more lower boiling part as end-capping reagent.Typical example, butane thiol have very much volatility and 200 DEG C be introduced into CIGS synthesis in because its boiling point be ~ 100 DEG C.But, butane thiol can be used as capping ligand and be used as sulphur source together with tertiary mercaptan.Another advantage of tertiary mercaptan is that they react with " cleaning ", such as, on final nano particle, do not remain any accessory substance.
Thus, an object of the present invention is to provide there is formula CuIn xga 1-xs 2nano particle, it is by alkanethiol capping ligand end-blocking, especially less than ten carbon and the alkanethiol capping ligand of preferred less than eight carbon.According to an embodiment, capping ligand has and is less than six carbon.According to an embodiment, capping ligand has four carbon.
After initial reaction, can at lower than the temperature (usually low ~ 40 DEG C) of reaction temperature by nano particle thermal annealing a period of time to improve topological structure and to make distribution of sizes narrow.
Use the nano particle general diameter of said method manufacture to be less than 10nm, more generally diameter is little of about 2.5nm.The method described provides the nanoparticle subgroup with high single dispersing degree.Such as, use the nano particle of method manufacture described to show to have and be less than about 200nm and be more preferably less than about 150nm or be less than the emission spectrum of FWHM of about 100nm.
After having reacted, nano particle can be separated by adding non-solvent and disperse to form nanoparticle inks in organic solvent is as toluene/chloroform and/or hexane again.The mercaptan of additive as extra can be added in reaction solution to adjust final ink viscosity.According to some embodiment, gained ink is formed the nano particle of q.s and black water based composition and comprise the nano particle that as many as is about 50%w/v, more preferably from about the nano particle of 10 to 40%w/v, and the nano particle of most preferably from about 20 to 30%w/v.According to other embodiment, nanoparticle concentration can be made high as much as possible.The nanoparticle concentration of adjustment ink is to adapt to most its operational factor in those skilled in the art's limit of power.
Nanoparticle inks can be printed onto on supporting layer to form the film comprising and introduce and be selected from the nano particle of the ion of periodic table the 11st, 13 and 16 race.Preferably, the formation of film passes through printing under being included in the condition allowing film to be formed on supporting layer, and the formula containing nano particle deposits on supporting layer by coating or spraying.Any suitable method can be used to realize the deposition of nanoparticles formulations, but it preferably include drippage casting (dropcasting), scraper for coating and/or spin coating.When using spin coating, the rotary speed of the highest about 5000rpm can be used to carry out spin coating, more preferably from about the rotary speed of 500 to 3500rpm, and the spin speed of most preferably from about 2000rpm.Alternatively or extraly, spin coating can be carried out within the as many as time period of about 300 seconds, the more preferably from about time period of 20 to 150 seconds, and most preferably from about time period of 60 seconds.
The preparation of film generally includes one or more anneal cycles, described anneal cycles comprises series of steps, wherein repeatedly increase the temperature of the nanoparticles formulations be deposited on supporting layer and at the temperature be increased to, maintain predetermined time section subsequently, then nanoparticles formulations being cooled to form film.Preferably, each step in series of steps tends to provide the temperature of about 10 to 70 DEG C of nanoparticles formulations to increase.Initial step can be carried out increase to provide the temperature larger than subsequent step.By way of example, the first step of step so can realize the temperature increase of about 50 to 70 DEG C, is then one or more steps subsequently, wherein temperature increase about 10 to 20 DEG C.Each step in series of steps preferably includes with the speed of as many as about 10 DEG C/min, more preferably with the speed of about 0.5 to 5 DEG C/min, and most preferably increases the temperature of nanoparticles formulations with the speed of about 1 to 2 DEG C/min.In an example, initial step can comprise rate temperature increase larger than subsequent step.Such as, in preferred embodiments, one or two of initial step can comprise heating to provide the temperature of about 8 to 10 DEG C/min to increase, and subsequent step can comprise the temperature increase of about 1 to 2 DEG C/min.As mentioned above, each step comprises heating and at the temperature be increased to, the formula containing nano particle is maintained predetermined time subsequently.
Embodiment 1-uses the CuInS of octanethiol 2the synthesis of nano particle
By Cu (OAc) (122.3mg, 0.9976mmol; OAc=acetic acid) and In (OAc) 3(292.0mg, 1.000mmol) to be blended in the 1-vaccenic acid of 5mL and 120 DEG C of heating 20 minutes.Mixture nitrogen is backfilled and the octanethiol injecting 5mL to manufacture yellow/orange suspension.Suspension be heated to 200 DEG C and maintain 1h at this temperature, during this, it reddens.To react and leave standstill annealing 17h at 170 DEG C, cool to room temperature also uses acetone separation product.By gained flocculate solids by collected by centrifugation, be redispersed in chloroform, filter, and with another precipitation circulation cleaning in acetone.The obvious exciton peaks at absorption spectrum (see Fig. 1) the 525nm place of the optically clear solution of nano particle, the absorption edge at about 640nm place, it is from block CuInS 2(810nm) obvious blue shift and with expection quantum limitation effect consistent.XRD figure (shown in Fig. 2 A) and published cubic CuInS 2mate well.
Embodiment 2-uses the CuInS of octanethiol 2the synthesis of nano particle
With 30.121gIn (OAc) 3(103mmol), 12.002gCu (OAc) (97.9mmol) and 180ml1-vaccenic acid load 1 liter of three neck round-bottomed flask of oven drying.Flask is equipped with Li Bixi (Liebig) condenser and uses purging with nitrogen gas.Mixture is also backfilled with nitrogen at 100 DEG C for degassed 1 hour subsequently.
The degassed 1-octanethiol of 140ml is added rapidly with syringe.Mixture is heated 30 minutes at 125 DEG C, heats 2 hours at 200 DEG C, be cooled to 160 DEG C subsequently and leave standstill annealing 16 hours.
By mixture cool to room temperature, subsequently flask is opened wide to air.Reactant mixture is rotated 5 minutes with 4000rpm.Dark-brown/orange supernatant is transferred to vial.
Solid dispersal is added 25ml acetone in 25ml toluene.Mixture is rotated 5 minutes with 4000rpm in centrifuges.Retain dark supernatant and extract sticky solid with other toluene and each 20ml of acetone.Again by centrifugation solid (4000rpm, 5 minutes).Supernatant and last merging and abandon solid.Add the methyl alcohol of 100ml and the acetone of 75ml to the supernatant merged, and mixture is rotated 3 minutes with 6500rpm.Abandon muddiness, grey orange supernatant retain remaining dark color, oily solid.
Main body to reaction solution is added 400ml methyl alcohol and 600ml acetone and mixture is rotated 5 minutes with 4000rpm.Abandon colorless supernatant liquid and retain dark oil, it uses methyl alcohol and each 400ml extracting twice of acetone further, is separated by the centrifugal of supernatant and decant at every turn.
Merge residual solid and use 200ml acetone rinsing, being dispersed in 100ml carrene subsequently completely.By the methanol acetone that adds 800ml1:1 product precipitated and pass through centrifugation.From methylene chloride/methanol (100:400ml), solid is precipitated again further.By centrifugal (4000rpm, 5 minutes) separating solids, drying under vacuo ~ 90 minutes, stores afterwards under a nitrogen.Collect the material of 39.479g.The element ratio being analyzed this compound of discovery by inductively coupled plasma optical emission spectra (ICP-OES) is Cu 1.0in 1.15s 1.70(by weight 13.09%Cu, 27.32%In, 11.22%S).Mercaptan end-capping reagent contribute to total sulfur content.Gained nano particle with the fluorescence peak at the absworption peak at ~ 510nm place and ~ 680nm place for feature, this and expect quantum limitation effect consistent (being Fig. 3 A and 3B respectively).
The peak (Fig. 2 B) of XRD figure mates with reference to the value of JCPDS32-0339 well with XRD, and can classify as the CuInS with tetragonal 2.The TEM image (Fig. 4) of nano particle shows the average-size of 2.5nm.
Embodiment 3-uses the CuInS of octanethiol and ODE:S 2the synthesis of nano particle
With 191.49gIn (OAc) 3(0.66mmol) load flask with 122.39gCu (OAc) (1.00mmol) and it is at room temperature placed in a vacuum.Inject the vaccenic acid of 5ml and gained green suspension is heated 20 minutes under vacuo at 100 DEG C.Backfill flask with nitrogen and inject the octanethiol (29mmol) of 5ml and temperature is elevated to 200 DEG C.Along with temperature increases, solution colour gradually becomes yellow, orange and finally become light red.Reaction solution is kept 10 minutes at 200 DEG C.
Meanwhile, the solution of the sulphur heating 1M under a nitrogen in 3 neck round-bottomed flasks in 1-vaccenic acid (ODE) is until all sulphur dissolves.This solution of 2.1ml (2.1mmol) to be injected in reaction solution and to keep 5 minutes at 200 DEG C.By reaction solution cool to room temperature and by collected by centrifugation red solid after adding 40ml acetone.Drying solid under vacuo.
Embodiment 4-uses the CuInS of octanethiol and TOP:S 2the synthesis of nano particle
With 1.25gIn (OAc) 3(4.28mmol), 0.51gCu (OAc) (4.2mmol) and 7.5ml1-vaccenic acid load 100 milliliter of three neck round-bottomed flask of oven drying.Flask is equipped with Liebig condenser and uses purging with nitrogen gas.Mixture is also being backfilled with nitrogen at 140 DEG C at 100 DEG C for degassed 1 hour subsequently for degassed 10 minutes subsequently.Add the 1-octanethiol of 5ml and mixture is heated at 180 DEG C.The 1.71MTOP:S solution of 5ml is added with the speed of about 7.5ml/hr.Heated solution 2 hours at 200 DEG C, subsequently 160 DEG C of annealing 18 hours.After annealing, interrupt heating and allowing reaction solution to be cooled to 60 DEG C.Adding the methyl alcohol of 40ml and gained mixture is at room temperature stirred 1 hour, is the 15-min period do not stirred subsequently.Described process is repeated once.Red solid is separated, washs with the acetone of 50mL and pass through centrifugation.By solid dispersal in the carrene of 30ml, filter and use the methyl alcohol of 75mL to precipitate again.Solid is redispersed in the carrene of 10mL, then precipitates and be separated.
The peak (Fig. 2 C) of XRD figure mates with reference to the value of JCPDS32-0339 well with XRD, and can classify as the CuInS with tetragonal 2.
The TGA figure of this material shows the second step (see Fig. 5) at 370 DEG C compared with the sample prepared in independent octanethiol.Although it is closely similar to which reflects total inorganic content, material in toluene with the visibly different behavior of material there is obviously more full-bodied TOP:S manufacturing.
Embodiment 5-uses the CuInS of hexadecanethiol 2the synthesis of nano particle
With 292.10gIn (OAc) 3, (1.00mmol), the vaccenic acid of 122.57Cu (OAc) and 5ml load flask and in 30 minutes at heating under vacuum to 120 DEG C.The hexadecanethiol of 8.8mL also adds in flask to manufacture yellow/orange suspension by the backfill of green suspension nitrogen.Suspension is heated to 270 DEG C and its color gradually becomes peony and finally becomes brown.After 1 hour, suspension cool to room temperature is added acetone with separating particles.Compared with synthesizing with in octanethiol (Fig. 6 B), hexadecanethiol (Fig. 6 A) allows to heat at higher temperatures but produces the nano particle had as the wider distribution of sizes as shown in absorption spectrum (Fig. 6).
Embodiment 6-Cu (In, Ga) S 2the synthesis of nano particle
By Cu (OAc) (1.48g, 12.1mmol), In (OAc) 3(2.82g, 9.66mmol), GaCl 3(1.28g, 7.27mmol) and ODE (25mL) to be filled in 250mL round-bottomed flask and at 100 DEG C degassed 2 hours.Add rapidly 1-octanethiol (18mL, 104mmol) and be warmed up to 125 DEG C, solution being annealed 30 minutes subsequently.Temperature be raised to 200 DEG C and solution annealed 2 hours.Before cool to room temperature, temperature is reduced to 160 DEG C and stirs and spend the night.
With the reactant mixture centrifugal 5 minute of 4000rpm by cooling.Top oily layer decant is abandoned.By solid dispersal in acetone, methyl alcohol is added subsequently and with by centrifugal for mixture 4000rpm 5 minutes.Solid to be redispersed in acetone/methanol and centrifugal.After abandoning supernatant, this process is repeated twice again.By dissolution of solid in carrene, precipitate by acetone/methanol subsequently.After centrifugal 5 minutes, supernatant is abandoned with 4000rpm.Repeat this process, subsequently by solid dried overnight under vacuo, retain black solid as product.
The following content based on weight is provided: 16.84%Cu, 25.25%In, 5.28%Ga, 18.8%S by the elementary analysis of ICP-OES.This meets stoichiometry CuIn 0.83ga 0.29s 2.21.Mercaptan end-capping reagent contribute to total sulfur content.
XRD (Fig. 2 D) shows distinctive chalcopyrite diffraction pattern, and peak position and relative intensity are at the CuInS from document 2and CuGaS 2those between.
The erose nano particle of TEM display ~ 4nm diameter, as shown in Figure 7.
Embodiment 7:Cu (In, Ga) S 2the synthesis of nano particle
By Cu (OAc) (1.48g, 12.1mmol), In (OAc) 3(2.82g, 9.66mmol), GaCl 3(0.73g, 4.1mmol) and ODE (25mL) to load in 250mL round-bottomed flask and at 100 DEG C degassed 1 hour.1-octanethiol (18mL, 104mmol) added fast and is warming up to 125 DEG C, solution being annealed 30 minutes subsequently.Temperature be increased to 200 DEG C and solution annealed 2 hours.Temperature is reduced to 160 DEG C before cool to room temperature and stirs and spend the night.
With the reactant mixture centrifugal 5 minute of 4000rpm by cooling.Top oily layer decant is abandoned.Solid (solid residue together with from reaction flask) by ultrasonic disperse in acetone, is then added methyl alcohol, with 4000rpm by centrifugal for mixture 5 minutes.Abandon supernatant.Solid to be scattered in again in acetone/methanol and centrifugal.After abandoning supernatant, process is repeated twice again.By dissolution of solid in carrene, then precipitate by acetone/methanol.After centrifugal 5 minutes of 4000rpm, abandon supernatant.Repeat this process, then that solid is dry under vacuo, leave black powder as product.
Following content is by weight given: 16.44%Cu, 24.63%In, 3.86%Ga, 17.67%S by the elementary analysis of ICP-OES.This corresponds to CuIn 0.83ga 0.21s 2.23stoichiometry.Mercaptan end-capping reagent contribute to total sulfur content.
Embodiment 8:Cu (In, Ga) S 2the synthesis of nano particle
By Cu (OAc) (1.48g, 12.1mmol), In (OAc) 3(2.82g, 9.66mmol), Ga (acac) 3(2.67g, 7.27mmol; Acac=acetylacetone,2,4-pentanedione) and ODE (25mL) to load in 250mL round-bottomed flask and 100 DEG C degassed 1 hour.Add rapidly 1-octanethiol (18mL, 104mmol) and be warming up to 125 DEG C, then solution being annealed 30 minutes.Be warming up to 200 DEG C and solution annealed 2 hours.Be cooled to 160 DEG C before cool to room temperature and stir and spend the night.
By the reactant mixture of cooling by ultrasonic disperse in acetone and use scraper by white solid manual separation and abandon.Methyl alcohol is added in solution, by mixture with 4000rpm centrifugal 5 minutes.Abandon supernatant.Solid to be scattered in again in acetone/methanol and centrifugal.After abandoning supernatant, repeat this process.By dissolution of solid in carrene, then precipitate by acetone/methanol.After centrifugal 5 minutes of 4000rpm, abandon supernatant.Repeat this process, then that solid is dry under vacuo, leave pale red brown ceramic powder as product.
The XRD (Fig. 2 E) of material shows distinctive chalcopyrite diffraction pattern, peak position and relative intensity from document CuInS 2and CuGaS 2those between.With with GaCl 3the CuInGaS of preparation 2compare peak and seem wider and more uncertain, showing can by the size using suitable Ga source to regulate particle.TEM shows the diameter of nano particle <3nm, as shown in Figure 8.
Following content is by weight given: 13.86%Cu, 22.05%In, 2.94%Ga, 19.98%S by the elementary analysis of ICP-OES.This corresponds to CuIn 0.88ga 0.19s 2.86stoichiometry.Mercaptan end-capping reagent contribute to total sulfur content.
Embodiment 9: Cu (In, the Ga) S using 1-octanethiol and sulphur powder 2the synthesis of nano particle
By Cu (OAc) (0.369g, 3.01mmol), In (OAc) 3(0.7711g, 2.64mmol), Ga (acac) 3(0.4356g, 1.19mmol), sulphur (0.2885g, 9.00mmol), benzyl oxide (15mL) and 1-octanethiol (13.8mL, 79.5mmol) are equipped with the 100mL round-bottomed flask of Liebig condenser and gatherer.Mixture is degassed 1 hour at 60 DEG C under vacuo.After nitrogen backfill, temperature be increased to 200 DEG C and keep 2 hours.Before cool to room temperature, solution be cooled to 160 DEG C and anneal 18 hours.Product toluene wash is used alcohol settling.
Embodiment 10: Cu (In, the Ga) S using 1-octanethiol and sulphur powder 2the synthesis of nano particle
By Cu (OAc) (0.369g, 3.01mmol), In (OAc) 3(0.7711g, 2.64mmol), Ga (acac) 3(0.4356g, 1.19mmol), sulphur (0.2885g, 9.00mmol) and oleyl amine (9mL) are equipped with the 100mL round-bottomed flask of Liebig condenser and gatherer.By mixture at 60 DEG C degassed 1 hour under vacuo.After nitrogen backfill, 1-octanethiol (4.8mL, 27.7mmol) is injected.Temperature be increased to 200 DEG C and keep 2 hours.Before cool to room temperature, solution be cooled to 160 DEG C and anneal 18 hours.Product toluene wash is used alcohol settling.
Embodiment 11:CuGaS 2the synthesis of nano particle
By Cu (OAc) (1.48g, 12.1mmol), GaCl 3(6.72g, 38.2mmol) and ODE (20mL) load 100mL round-bottomed flask and at 100 DEG C degassed 1 1/ 2hour.Add 1-octanethiol (18mL, 104mmol) and be warming up to 200 DEG C, then solution being annealed 2 hours.Be cooled to 160 DEG C before cool to room temperature and stir and spend the night.
By the reactant mixture with 4000rpm centrifugal 5 minutes of cooling.Top oily layer decant is abandoned.By solid dispersal in acetone, then add methyl alcohol, by mixture with 4000rpm centrifugal 5 minutes.Solid to be scattered in again in acetone/methanol and centrifugal.After abandoning supernatant, repeat this process.Solid acetone rinses twice again.By dissolution of solid in carrene (DCM), then precipitate by acetone/methanol.After centrifugal 5 minutes of 4000rpm, abandon supernatant.Repeat this process, then by solid drying about 3 hours under vacuo.By the other two parts DCM/ washed with methanol of oily solid, then dried overnight, leaves dark-brown oily solid as product.
Following content is by weight given: 12.74%Cu, 13.42%Ga, 11.54%S by the elementary analysis of ICP-OES.This corresponds to CuGa 0.96s 1.90stoichiometry.Mercaptan end-capping reagent contribute to total sulfur content.
XRD (Fig. 2 F) shows distinctive chalcopyrite diffraction pattern, its with from the CuGaS of document 2peak position and relative intensity well corresponding.
TEM (Fig. 9) shows has ~ the aggregation of the pseudo-nano spherical particle of the average diameter of 4-5nm.
Embodiment 12: the CuInS using tertiary nonane mercaptan 2the synthesis of nano particle
By 5.003g (17.1mmol) In (OAc) 3, 2.005g (16.3mmol) Cu (OAc) and 30ml benzyl oxide load the 100ml round-bottomed flask of oven drying.Flask be equipped with Liebig condenser and collect head, and with nitrogen backfill before in 1 hour at heating under vacuum to 100 DEG C.
At 100 DEG C, add the butane thiol of 9ml (84mmol) and mixture is stirred other 30 minutes.Add the tertiary nonane mercaptan of 13ml (69mmol) subsequently and mixture be heated to 140 DEG C and left standstill stirring 4 hours before allowing to be cooled to room temperature.
When cool to room temperature, with vigorous stirring 30ml propan-2-ol is joined in reactant mixture, and flask is opened wide to air.With 5400G mixture rotated 3 minutes and retain dark supernatant.Remaining residue is dispersed in 10ml toluene and then adds 10ml propan-2-ol twice.After each dispersion, with 5400G mixture rotated 3 minutes and merge all supernatants.Remaining residue is abandoned after twice washing.
Methyl alcohol (300ml) is joined merging supernatant and by centrifugation (2700G, 5 minutes) gained sediment.Abandon light orange supernatant, and solid is being precipitated from 10ml carrene/100ml methyl alcohol before drying by centrifugation with under vacuo again.
According to TGA (Figure 10), the method produces the material that 4.585g has inorganic content 67%.Inorganic content is higher than the CuInS synthesized with straight chain octanethiol 2, this confirms that the part of more short chain makes carbon content less in nano particle become possibility.
Absorption and photoluminescence spectra (being Figure 11 A and 11B respectively) show the representative quantum restriction of nano particle.XRD figure and the known CuInS of Fig. 2 G particle 2xRD figure very relevant.Following content is by weight given: 16.40%Cu, 33.24%In, 23.41%S by the elementary analysis of ICP-OES.This corresponds to CuIn 1.20s 2.80stoichiometry.Mercaptan end-capping reagent contribute to total sulfur content.
Embodiment 13: Cu (In, the Ga) S using tertiary nonane mercaptan 2the synthesis of nano particle
By 3.529g (12.1mmol) In (OAc) 3, 1.901g (5.2mmol) Ga (acac) 3, 3.227g (16.2mmol) Cu (OAc) 2h 2o, 22.5ml oleyl amine and 30ml benzyl oxide load the 250ml round-bottomed flask of oven drying.Flask be equipped with Liebig condenser and collect head, and with nitrogen backfill before in 1 hour at heating under vacuum to 100 DEG C.
Add degassed 1-octanethiol (12ml, 69mmol) at 100 DEG C and mixture leaves standstill stirring 15 minutes, add the degassed tertiary nonane mercaptan of 13ml (69mmol) subsequently.Before allowing to be cooled to room temperature, mixture was heated to 160 DEG C in 4.5 hours.
When cooling, flask being opened wide to air and then adds 50ml propan-2-ol.With 2700G mixture rotated 5 minutes and retain wine-colored supernatant.Remaining residue is dispersed in 20ml toluene, adds the propan-2-ol of 40ml at this moment, and dispersion process rotates 5 minutes with 2700G and supernatant and suspension before merged.Abandon remaining residue.
Methyl alcohol (250 milliliters) is joined merging supernatant and by mixture with 2700G centrifugal 5 minutes.Abandon light orange supernatant and gained solids is dispersed in 30ml toluene.Add propan-2-ol (45 milliliters) and mixture is rotated 5 minutes with 2700G.Retain supernatant, and abandon the residue stayed.Methyl alcohol (150 milliliters) is joined supernatant and by centrifugation gained flocculate solids (2700G, 5 minutes), then precipitate again from carrene (30ml)/acetone (60ml)/methyl alcohol (180 milliliters), then precipitate again from carrene (30ml)/methyl alcohol (150 milliliters).Sediment is also dry under vacuo by centrifugation.
According to TGA (Figure 12), the method produces the material that 5.962g has inorganic content 57%.Absorption and photoluminescence spectra (being Figure 13 A and 13B respectively) show the representative quantum restriction of nano particle.Following content is by weight given: 13.93%Cu, 20.42%In, 4.74%Ga, 15.97%S by the elementary analysis of ICP-OES.This corresponds to CuIn 0.81ga 0.31s 2.80stoichiometry.
It should be pointed out that the boiling at the temperature (~ 350 DEG C) higher than the solvent used in embodiment before of the solvent oleyl amine that uses in this embodiment.But according to TGA (Figure 12) display of nano particle prepared by the method described in this embodiment, all organic substances relevant with nano particle evaporate at lower than the temperature of 350 DEG C, and this shows oleyl amine not by nano particle end-blocking.Thus, oleyl amine is not bonded in the film using the nano particle manufactured according to this method to prepare, and does not contribute carbon remaining in film yet.
Although illustrate and described specific embodiment of the invention scheme, they have been not intended to limit the scope that the present invention is contained.Understanding can make a variety of changes when not departing from the scope of invention of open support and revise by those skilled in the art.

Claims (19)

1. comprise a composition for nanoparticle subgroup, described nano particle has empirical formula CuIn xga 1-xs 2wherein (0<x<1), wherein each nano particle comprises the organic ligand layer being attached to described nanoparticle surface, and wherein said organic ligand layer is made up of mercaptan substantially.
2. composition according to claim 1, wherein said mercaptan comprises less than ten carbon atoms.
3. composition according to claim 1, wherein said mercaptan comprises less than eight carbon atoms.
4. composition according to claim 1, wherein said mercaptan comprises less than six carbon atoms.
5. composition according to claim 1, wherein when described nano particle is heated to the temperature lower than 300 DEG C, sprays described mercaptan from described nano particle.
6. composition according to claim 1, wherein said mercaptan has the boiling point lower than 200 DEG C.
7. composition according to claim 1, wherein said mercaptan has the boiling point lower than 150 DEG C.
8. composition according to claim 1, wherein said mercaptan has the boiling point lower than 100 DEG C.
9. composition according to claim 1, wherein said group's display has the emission spectrum of the FWHM lower than about 200nm.
10. composition according to claim 1, wherein said group's display has the emission spectrum of the FWHM lower than about 100nm.
11. 1 kinds of methods for the preparation of nano particle, described method comprises: by mantoquita, indium salt, and gallium salt and mercaptan mix and in organic solvent by described solvothermal to the temperature being not more than 220 DEG C.
12. methods according to claim 11, wherein said temperature is not more than 200 DEG C.
13. methods according to claim 11, wherein said temperature is not more than 150 DEG C.
14. methods according to claim 11, described method also comprises adds the solution of TOP:S to described solvent.
15. methods according to claim 11, wherein said mercaptan has the boiling point lower than 150 DEG C.
16. methods according to claim 11, wherein said mercaptan has the boiling point lower than 100 DEG C.
17. methods according to claim 11, wherein said mercaptan comprises less than ten carbon atoms.
18. methods according to claim 11, wherein said mercaptan comprises less than eight carbon atoms.
19. methods according to claim 11, wherein said mercaptan comprises less than six carbon atoms.
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